Disposable hazardous and radioactive liquid aqueous waste composition and method

ABSTRACT

An improved method of disposing of radioactive or hazardous liquid aqueous waste compositions having a substantial amount of dissolved solids comprises mixing the liquid under a high mechanical shear with a clay selected from the group consisting of attapulgite, sepiolite, and mixtures thereof. Water soluble or miscible organic liquids as well as liquid hydrocarbon mixtures thereof may also be solidified by utilizing the aforesaid clays together with an organic ammonium montmorillonite having at least 10 carbon atoms, the amount of montmorillonite used being proportional to the amount of liquid hydrocarbon present.

REFERENCE TO OTHER APPLICATIONS

This is a continuation of co-pending application Ser. No. 06/821,906,filed Jan. 23, 1986, now abandoned, and a continuation-in-part of myapplication Ser. No. 818,323, filed Jan. 13, 1986 .Iadd., now abandoned..Iaddend.

BACKGROUND OF THE INVENTION

The disposal of hazardous and radioactive waste materials is of extremeimportance. Federal and state laws and requirements covering suchdisposals are particularly severe and stringent due to the dangers toplant and animal life if the desired standards are not met and thehazardous or radioactive materials become exposed to the environment.Because of the potential dangers, the United States Nuclear RegulatoryCommission has not only identified the hazardous and radioactivematerials to date, which list is continually being amended and updated,but has set forth specific standards and requirements for protecting theenvironment against such waste materials. The resulting laws andregulations are set forth in 10 CFR, particularly sections 1-199. Otherregulations relating to transportation, packaging, labeling andidentifying hazardous and radioactive materials are also found in 40CFR, 1-799 and 49 CFR. 100-177. Other publications which relate toclassifying, indexing and discussing radioactive and hazardous wastematerials include DOE/LLW-14T publication "Waste Classification, AProposed Methodology For Classifying Low-Level Radioactive Waste", Dec.1982, DOE/LLW-17T, "Survey of Chemical And Radiological IndexesEvaluating Toxicity" , March 1983, FW-874, "Hazardous Waste LandTreatment", April 1983 FW-872 "Guide To The Disposal Of ChemicallyStabilized and Solidified Waste", Sept. 1982.

It is the common practice to process the liquid hazardous or radioactivematerials by adding absorbents in an attempt to enhance handling andtransportation, as well as eventual storage thereof. The materials thathave been used heretofore include diatomaceous earth, vermiculite orexpanded mica such as zonolite and krolite, portland and gypsum cements,as well as clay materials such as calcium bentonites. A problem withsuch materials is that only a relatively small amount of liquid can beabsorbed or otherwise treated with less than satisfactory results. Forexample, liquid materials are desirably transported and disposed of in55 gallon drums. However, it has been found with the use of theseabsorbents, solid compositions cannot be achieved or if temporarilyachieved, liquid separation occurs during transportation or storage. Anyseparated or free-standing liquids are especially undesirable because ofthe potential danger of leakage from a ruptured or opened container. Itis to the substantial elimination of such problems that the presentinvention is directed.

In prior co-pendin application Ser. No. 743,057, filed Jul. 10, 1985,(abandoned) is disclosed an improved method of substantially solidifyinghazardous or radioactive aqueous liquid compositions using a specialsodium montmorillonite high in sodium content. As effective as thatmaterial is in achieving desired solidification of aqueous radioactiveor hazardous compositions, its suitability for use with water-based oraqueous compositions containing large amounts of dissolved solids,especially those exceeding about 20,000 parts per million issubstantially diminished. Moreover, the sodium montmorillonite is not aseffective in solidifying the hazardous or radioactive organic liquidssuch as polyols or polyglycols, or other similar water soluble ormiscible organic liquids and aqueous or hydrocarbon mixtures thereof. Itis to the substantial solidification of such liquid materials that thepresent invention is directed.

SUMMARY OF THE INVENTION

An improved method of treating hazardous and radioactive liquid wastescomprises mixing the waste materials with a clay selected from the groupconsisting of attapulgite, sepiolite, and mixtures thereof in suitableproportions and stirring the mixture under high mechanical shear toproduce a substantially solidified composition. The clay material mayalso be used with an organic ammonium montmorillonite, especially usefulwhere the waste liquid includes liquid hydrocarbons. In addition, wheremoderate amounts of dissolved solids are present in aqueous wastematerials, the clay may also be mixed with sodium montmorillonite. Theresulting substantially solidified waste material may be handled,transported and stored under a variety of conditions for extendedperiods of time without evidence of liquid separation or deterioration.These and other advantages as well as the specific materials used in theinvention will be more particularly described in the following detaileddescription.

DETAILED DESCRIPTION OF THE INVENTION

The method of solidfying the hazardous and radioactive liquid wastecompositions according to the invention applies to a great variety ofsuch materials, especially aqueous solutions and mixtures containingsubstantial amounts of dissolved solids, water soluble or miscibleliquids, and aqueous or hydrocarbon mixtures thereof. Many radioactiveor hazardous waste liquids contain at least 20,000 parts per million ofdissolved solids. Such liquids are difficult to effectively treat forsolidification for storage by using sodium montmorillonite as disclosedin the aforesaid co-pending application Ser. No. 743,057 (nowabandoned). Especially problematic are dissolved calcium, magnesium,iron and aluminum salts. Large amounts of dissolved chloride and sulfatesalts also substantially reduce the solidifying efficiency of the sodiummontmorillonite.

Another group of liquid materials to which the invention is particularlyeffective are water soluble or miscible organic liquids commonly used inpharmaceuticals, detergents and as non-petroleum lubricants. Examples ofsuch materials include polyols such as polyhydric alcohols, alkyleneglycols, especially ethylene glycol, glycerol, polyglycerols andpolyglycerol esters, and polyglycols such as polyalkylene glycols,particularly polyethylene glycol. These liquids may be found inhazardous or radioactive wastes combined with aqueous or hydrocarboncompositions including reactor plant organic liquids such as turbine,cutting and lubricating oils, solvent sludges which are used to degreasereactor components such as Freon TF, cleaning solvents such as Stoddardsolvents, and decontamination solvents. In addition, a great quantity ofsuch wastes are aqueous liquids, containing over about 95% watercontaminated with radioactive materials such as greases from reactorplant turbines. Hospital-sourced contaminated liquids containradioactive materials used in cancer treatments. From such sources,particularly common radioactive materials include radioactive cobaltssuch as cobalt 57, cobalt 58 and cobalt 60, cesium, plutonium anduranium isotopes, and the like. However, it is to be understood,according to the invention, that any radioactive materials that are tobe disposed of and are defined in the aforesaid laws, regulations, anddocuments are intended to be included in the compositions treatedaccording to the method of this invention, as well as any lateridentified and added radioactive materials, regardless of source andregardless of the specific radioactive material or radioisotope.

Common hazardous waste materials include acids, bases, chlorinatedhydrocarbons including PCB, dioxins, and the like. Again, these as wellas the radioactive materials may be in aqueous liquids, particularlythose having 95% or more water, or they may be aqueous mixturescontaining up to substantial amounts of hydrocarbons. In addition to theabove-described water soluble or water miscible liquids which may betreated according to the invention are aldehydes, ketones, acids,ethers, together with a great number of nitrogen, phosphorous and sulfurcontaining inorganic and organic compounds. By the term water miscibleor water soluble as used herein it is intended to cover any of suchmaterials which are "hazardous" or present in radioactive liquid wastesas previously defined. Moreover, as used herein, "hydrocarbons" isintended to define any such oils, solvents and other hydrocarbons ornon-aqueous liquids as generally described above which have beencontaminated with radioactive materials or which themselves areconsidered hazardous chemicals according to governmental regulations.

The material used in the method of the present invention for treatingthe above-described hazardous and radioactive liquid waste materials isa clay selected from the group consisting of attapulgite, sepiolite, andmixtures thereof. Attapulgite is a hydrated magnesium aluminum silicate,a clay material. Sepiolite, sometimes referred to as meerschaum, is anatural hydrous magnesium silicate. The preferred materials are thosewhich meet the American Petroleum Institute specification for oil-welldrilling-fluid materials, such as set forth in API Spec 13A, 11thEdition Jul. 1, 1985, Sections 5 and 6. The amount of clay used, whichmay be either one or a mixture of the aforesaid clays is between about2.2 and about 5.0 pounds per gallon of aqueous solution or water solubleor miscible organic liquid or mixtures thereof. Again, the use of theseclays is particularly desirable and useful in solidifying aqueoussolutions having substantial amounts of dissolved solids content, aboveabout 20,000 to 50,000 parts per million or higher. Water soluble ormiscible organic liquids which may be solidified by the clays of theinvention are as previously described. Of special importance in theaforesaid group of organic liquids is ethylene glycol, used extensivelyas a coolant and antifreeze material, and glycerol.

In using the aforesaid clays to substantially solidify the liquidwastes, be they aqueous, water soluble or miscible organic liquids, ormixtures thereof, it is necessary to subject the composition tosubstantial mechanical shear forces to produce the requiredsolidification. This may be carried out by subjecting the liquidcomposition with the clay added thereto in the aforesaid proportions tostirring of at least about 500 rpm, and more preferably at about 1,000rpm or greater. Such shearing forces are necessary to dissociate themineral aggregates and impart the desired characteristics to achieve thedesired solidification. At the shearing forces realized by stirring at1,000 rpm or more, it is usually only necessary to subject the mixturesto the shear forces for a few minutes, up to about 5 to 10 minutes inorder to effect solidfication. By the term "solidified" or"substantially solidified" herein it is intended to define a materialwhich is not pourable.

When solidifying an aqueous liquid waste having a more moderate amountof dissolved solids, such as between about 5,000 and about 30,000 partsper million, it has been found that by using a sodium montmorillonite incombination with either or both of the aforesaid clays, substantialsolidification or stiffness may be obtained using a smaller amount oftotal solidification agent mixture than if the attapulgite or sepioliteclays are used alone. For example, it has been found that bysubstituting between about 5 and about 45% of the attapulgite orsepiolite with sodium montmorillonite, the total amount of solidifyingagent required to achieve solidification may be reduced by up to 25% orso. Preferred amounts of sodium montmorillonite used in this embodimentwill be between about 20 and 33% of the total solidifying compositionmixture. In this embodiment, the total amount of sepiolite orattapulgite combined with sodium montmorillonite, added is convenientlybetween about 1.5 and about 4.0 pounds per gallon of the liquid.

The sodium montmorillonite to be used contains a major portion of sodiumas the exchangeable cation. Such a preferred sodium montmorillonite isdescribed in copending U.S. application Ser. No. 743,057, filed Jun. 10,1985, (abandoned), the description thereof incorporated herein byreference Accordingly, the preferred sodium montmorillonite used hasover about 50% and more preferably above about 60 meq %.

In another embodiment of the invention the aforesaid water soluble ormiscible organic liquids mixed with liquid hydrocarbon wastes aresolidified by combining either the attapulgite or sepiolite clays ormixtures thereof with an organic ammonium montmorillonite disclosed inmy co-pending application Ser. No. 818,323 filed Jan. 13, 1986, thedescription thereof incorporated herein by reference. The organicammonium montmorillonites are reaction products of sodiummontmorillonite with an amine, amine salt or quaternary ammonium saltand are prepared by methods described in U.S. Pat. Nos. 2,531,427 and2,966,506, also incorporated herein by reference. Preferred organicammonium montmorillonites contain at least 10 carbon atoms in theorganic portion of the montmorillonite with a readily available anduseful material being dimethyl dihydrogenated tallow ammoniummontmorillonite The mixtures of hydrocarbon and the water miscible orsoluble organic liquids in which this combination of soildifyingmaterials is useful contains between about 5 and 95% of hydrocarbonbased on the liquid mixture, by volume. In solidifying such a liquid,the ratio of clay:organic ammonium montmorillonite is about directlyproportional to the ratio of the organic liquid:liquid hydrocarbonpresent by volume, respectively. Moreover, the amount of clay andorganic ammonium montmorillonite mixture is preferably between about 2.5and about 5.5 pounds per gallon of the bulk liquid being solidified.Again, as previously described, the liquid mixture will be subjected tothe high shear stirring in order to achieve the desired solidification.

In solidifying the aforesaid hydrocarbon containing liquids,solidification may also be enhanced by utilizing a small amount of polarorganic compound. The suitable polar organic compounds are thosedescribed in my aforesaid co-pending application and are incorporatedherein by reference. Most preferred materials are the lower molecularweight alcohols having between one and about 8 carbon atoms,particularly methyl alcohol, ethyl alcohol, n-propyl alcohol andisopropyl alcohol. The amount of polar organic compound used will bebetween about 1 and about 10% based on the volume of liquid hydrocarbon.Of course, where the waste liquid already includes a polar organiccompound, which list includes the alcohols, carbonates, acetates,ethers, ketones, benzoates and halegenated carbons having between about1 and about 10 carbon atoms, it will not be necessary to add additionalpolar material. However, when it is desirable to add the polar organiccompound, amounts of between 1 and about 10%, by volume, based on thehydrocarbon present in the waste mixture will be suitable.

In treating the waste liquid composition to obtain solidification, aspreviously noted, it is convenient to place about 45 gallons of thewaste liquid into a 55 gallon drum. The clay material, whether it besepiolite, attapulgite, mixtures thereof, or mixtures of those clayswith sodium montmorillonite or organic ammonium montmorillonite aspreviously described, is added with stirring of the aforesaid mechanicalshear forces until substantial solidification is achieved. Thesolidification material is preferably added together although it may beadded separately. After the composition has been stirred for the desiredamount of time, usually a few minutes will be sufficient, it may beallowed to stand for a period of time after it has been "set up",normally about 24 hours, and then inspected to see if any liquid hasseparated. If additional solidification is needed, more of thesolidification materials may be added with additional stirring tocomplete the solidification process.

By way of example, different liquid hazardous waste materials weretreated in laboratory equivalents of the following:

EXAMPLE I

To 45 gallons of pure ethylene glycol was added pounds of attapulgite.The mixture was stirred at about 1000 rpm for about 5 minutes resultingin a thick, stiff, unpourable composition. The same result was achievedsubstituting sepiolite as the solidfying agent.

By way of comparison, 350 pounds of sodium montmorillonite was requiredto solidify 25 gallons of the ethylene glycol to substantially the samesolid consistency.

EXAMPLE II

A 40 gallon sample of a 20% aqueous sodium chloride and stirred outsolution was mixed with 190 pounds of sepiolite 1000 rpm for 5 minutesto achieve a thick, stiff, unpourable composition. The same result wasachieved substituting attapulgite for the sepiolite.

By comparison, 300 pounds of sodium montmorillonite was required tosolidify 30 gallons of the 20% sodium chloride solution.

EXAMPLE III

Forty-five gallons of an 8% aqueous sodium chloride solution was mixedwith 225 pounds attapulgite and stirred at 1000 rpm for 5 minutes toachieve a stiff, substantially solidified material.

To another 45 gallon sample of the aqueous 8% sodium chloride solutionwas added a mixture of 120 pounds attapulgite and 60 pounds sodiummontmorillonite with stirring at 1000 rpm to obtain a substantiallysolid composition of the same consistency.

The tests were repeated substituting sepiolite for attapulgite withsubstantially the same results.

I claim:
 1. A method of disposing of radioactive or hazardous liquidwastes comprising a water soluble or miscible organic liquid, an aqueoussolution having a dissolved solids content of about 5,000 parts permillion or more, and mixtures thereof comprising adding thereto betweenabout 2.2 and about 5.0 pounds of a clay selected from the groupconsisting of attapulgite, sepiolite, and mixtures thereof per gallon ofsaid liquid and stirring the mixture under high mechanical shear untilit is substantially solidified.
 2. The method of claim 1 wherein saidcomposition is subjected to high shear stirring of at .[.lease.]..Iadd.least .Iaddend.about 500 rpm.
 3. The method of claim 1 whereinsaid composition is subjected to high shear stirring of at least about1,000 rpm. .[.4. A method of disposing of radioactive or hazardous watersoluble or miscible organic liquids and having between about 5% andabout 95% liquid hydrocarbon by volume, comprising mixing said liquidwith a mixture of clay selected from the group attapulgite, sepiolite,and mixtures thereof and an organic ammonium montmorillonite having atleast 10 carbon atoms at a ratio of clay:organic ammoniummontmorillonite about directly proportional to the ratio of said organicliquid:liquid hydrocarbon, by volume, respectively, and wherein theamount of said clay and organic ammonium montmorillonite mixture isbetween about 2.5 and about 5.5 pounds per gallon of total bulk liquid,and stirring the mixture under high mechanical shear until it issubstantially solidified..].
 5. .[.The method of claim 4 includingadding.]. .Iadd.A method of disposing of radioactive or hazardous watersoluble or miscible organic liquids and having between about 5% andabout 95% liquid hydrocarbon by volume, comprising mixing said liquidwith a mixture of clay selected from the group consisting ofattapulgite, sepiolite, and mixtures thereof and an organic ammoniummontmorillonite having at least 10 carbon atoms, at a ratio ofclay:organic ammonium montmorillonite about directly proportional to theratio of said organic liquid:liquid hydrocarbon, by volume,respectively, and wherein the amount of said clay and organic ammoniummontmorillonite mixture is between about 2.5 and about 5.5 pounds pergallon of total bulk liquid, and .Iaddend.between about 1 and about 10%by volume of a polar organic compound based on the hydrocarbon.[...]..Iadd., and stirring the mixture under high mechanical shearuntil it is substantially solidified. .Iaddend. .[.6. The method ofclaim 4 including adding.]. .Iadd.A method of disposing of radioactiveor hazardous water soluble or miscible organic liquids and havingbetween about 5% and about 95% liquid hydrocarbon by volume, comprisingmixing said liquid with a mixture of clay selected from the groupconsisting of attapulgite, sepiolite, and mixtures thereof and anorganic ammonium montmorillonite having at least 10 carbon atoms, at aratio of clay:organic ammonium montmorillonite about directlyproportional to the ratio of said organic liquid:liquid hydrocarbon, byvolume, respectively, and wherein the amount of said clay and organicammonium montmorillonite mixture is between about 2.5 and about 5.5pounds per gallon of total bulk liquid, and .Iaddend.between about 1 andabout 10% of an alcohol having between 1 and 3 carbon atoms based on thehydrocarbon .[...]..Iadd., and stirring the mixture under highmechanical shear until it is substantially solidified. .Iaddend.
 7. Amethod of disposing of an aqueous radioactive or hazardous liquid havinga dissolved solids content of between about 5,000 and about 30,000 partsper million comprising adding thereto a mixture of between about 55% andabout 95% of a clay selected from the group consisting of attapulgite,sepiolite, and mixtures thereof and between about 5% and about 45%, byweight, sodium montmorillonite having sodium as the major exchangeablecation, said mixture added in an amount of between about 1.5 and about4.0 pounds per gallon of said liquid, and stirring the mixture underhigh mechanical shear until it is substantially solidified.
 8. Asubstantially solidified hazardous or radioactive composition consistingessentially of water soluble or miscible organic liquid, an aqueoussolution having a dissolved solids content of at least about 20,000parts per million, and mixtures thereof, and between about 2.2 and about5.0 pounds of a clay selected from the group consisting of attapulgite,sepiolite, and mixtures thereof per gallon of liquid.
 9. The compositionof claim 8 wherein said water soluble or miscible organic liquid isselected from the group consisting of polyhydric alcohols, glycyerols,and plyalkylene glycols.
 10. A substantially solidified hazardous orradioactive composition consisting essentially of an aqueous solutionhaving between about 5,000 and about 30,000 parts per million dissolvedsolids and a mixture of between about 55% and about 95% by weight of aclay selected from the group consisting of attapulgite, sepiolite, andmixtures thereof, and between about 5% and about 45%, by weight sodiummontmorillonite having sodium as the major cation said mixture of saidclay and sodium montmorillonite being present in an amount of betweenabout 1.5 and about 4.0 pounds per gallon of said liquid.
 11. Thecomposition of claim 10 including between about 5 and about 95% byvolume based on said aqueous solution of a water soluble or miscibleorganic waste liquid selected from the group consisting of aldehydes,ketones, acids, ethers, esters, alcohols, polyols and polyglycols..[.12. A substantially solidified hazardous or radioactive compositionconsisting essentially of a water soluble or miscibel organic liquid anda liquid hydrocarbon and a mixture of a clay selected from the groupconsisting of attapulgite, sepiolite, and mixtres thereof and an organicammonium montmorillonite having at least 10 carbon atoms wherein saidamount of said clay and said organic ammonium montmorillonite is betweenabout 2.5 and about 5.5 pounds per gallon of said liquid..]. .[.13. Thecomposition of claim 12 wherein the liquids comprise between about 5%and about 95% organic liquid and between about 5% and about 95% liquidhydrocarbon, by volume, and wherein the ratio of said clay:organicammonium montrmorillonite is about directly proportional to the ratio ofsaid organic liquid:liquid hydrocarbon, respectively..].
 14. The methodof claim 1 including substituting between about 5 and about 45% of saidclay with sodium montmorillonite. .Iadd.15. A method of disposing ofradioactive or hazardous liquid wastes comprising a water soluble ormiscible organic liquid, an aqueous solution and mixtures thereofcomprising adding thereto between about 2.2 and about 5.0 pounds of aclay selected from the group consisting of attapulgite, sepiolite, andmixtures thereof per gallon of said liquid and stirring the mixtureunder high mechanical shear until it is substantially solidified..Iaddend. .Iadd.16. A method of disposing of an aqueous radioactive orhazardous liquid comprising adding thereto a mixture of between about55% and about 95% of a clay selected from the group consisting ofattapulgite, sepiolite, and mixtures thereof and between about 5% andabout 45%, by weight, sodium montmorillonite having sodium as the majorexchangeable cation, said mixture added in an amount of between about1.5 and about 4.0 pounds per gallon of said liquid, and stirring themixture under high mechanical shear until it is substantiallysolidified. .Iaddend. .Iadd.17. A substantially solidified hazardous orradioactive composition consisting essentially of water soluble ormiscible organic liquid, an aqueous solution, and mixtures thereof, andbetween about 2.2 and about 5.0 pounds of a clay selected from the groupconsisting of attapulgite, sepiolite, and mixtures thereof per gallon ofliquid. .Iaddend. .Iadd.18. A substantially solidified hazardous orradioactive composition consisting essentially of an aqueous solutionand a mixture of between about 55% and about 95% by weight of a clayselected from the group consisting of attapulgite, sepiolite, andmixtures thereof, and between about 5% and about 45%, by weight sodiummontmorillonite having sodium as the major cation said mixture of saidclay and sodium montmorillonite being present in an amount of betweenabout 1.5 and 4.0 pounds per gallon of said liquid. .Iaddend.